CN117247578A - 一种新型复合改性重质碳酸钙用于pbat/pla薄膜的制备方法 - Google Patents
一种新型复合改性重质碳酸钙用于pbat/pla薄膜的制备方法 Download PDFInfo
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 147
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 67
- 239000002131 composite material Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229920006381 polylactic acid film Polymers 0.000 title claims abstract description 20
- 229920001896 polybutyrate Polymers 0.000 title claims abstract 15
- 229920000747 poly(lactic acid) Polymers 0.000 claims abstract description 27
- 239000004970 Chain extender Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
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- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 9
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 9
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- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 9
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- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 claims description 5
- AXKZIDYFAMKWSA-UHFFFAOYSA-N 1,6-dioxacyclododecane-7,12-dione Chemical compound O=C1CCCCC(=O)OCCCCO1 AXKZIDYFAMKWSA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002635 polyurethane Polymers 0.000 claims description 4
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- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 4
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- ZMKVBUOZONDYBW-UHFFFAOYSA-N 1,6-dioxecane-2,5-dione Chemical compound O=C1CCC(=O)OCCCCO1 ZMKVBUOZONDYBW-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001634 Copolyester Polymers 0.000 description 1
- 208000034530 PLAA-associated neurodevelopmental disease Diseases 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
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- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N carbon dioxide Natural products O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
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- HSBFHUOJEGKWRL-KVVVOXFISA-N ethanol;(z)-octadec-9-enoic acid Chemical compound CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O HSBFHUOJEGKWRL-KVVVOXFISA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
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- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002362 mulch Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
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- 239000004629 polybutylene adipate terephthalate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
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- 229920005996 polystyrene-poly(ethylene-butylene)-polystyrene Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000009461 vacuum packaging Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/021—Calcium carbonates
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
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Abstract
本发明公开一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,具体为用一定量的丙烯酸马来酸共聚物和油酸对重质碳酸钙进行复合表面改性,改性剂质量分数设置为1%,将改性后的碳酸钙、PBAT、PLA、扩链剂、抗氧剂等按照一定比例混合均匀后,用双螺杆挤出机共混并吹膜,得到复合材料薄膜。本发明所述一种复合改性重质碳酸钙用于高填充PBAT/PLA薄膜及其制备方法中,制备方法简单,在高填充的情况下复合材料薄膜仍能保证优异的力学性能兼具了成本低性能优异的特点。
Description
技术领域
本发明涉及高分子材料技术领域,具体涉及一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法。
背景技术
在最受欢迎的薄膜材料中,石油基塑料制品多年来被广泛使用,如农用地膜、快递包装、食品真空包装袋等。然而,严重的生态环境“白色污染”问题越来越引起人们的关注。为了最大程度地减少传统的不可生物降解聚合物对环境的负面影响,可生物降解的替代材料已引起越来越多的关注,特别是来源于可再生资源的聚合物受到了高度关注。目前,市场上比较常见的生物降解材料有聚乳酸(PLA)、聚己二酸/对苯二甲酸丁二酯(PBAT)、聚己内酯(PCL)、聚丁二酸丁二酯(PBS)、聚羟基脂肪酸脂类(PHAs)及二氧化碳共聚物(PPC)等。
聚己二酸-对苯二甲酸丁二酯 (PBAT) 是一种完全可生物降解的脂肪族和芳香族共聚酯,其既有较好的延展性和断裂伸长率,也有较好的耐热性和冲击性能和优良的生物降解性。但其熔体粘度大、结晶速率低、抗拉强度低、成本高等缺点制约了其加工性能和工业应用。在与PBAT共混时,聚乳酸(PLA) 是以乳酸为主要原料聚合得到的聚酯类聚合物,具有良好的抗拉强度及延展度,热稳定性好。而碳酸钙作为无机填料,在应用到塑料中可以大大降低制作成本,同时改性过后的碳酸钙也可以改善高分子材料的很多性能,比如:可以提高的塑料的硬度和刚度;提高塑料的热稳定性;改进塑料的加工性能、平滑度、收缩率等。但是碳酸钙在高分子材料中容易团聚,相容性差,从而随着用量的增加导致复合材料的力学性能反而下降,且大部分的改性碳酸钙方法复杂且不易工业化。
因此,寻找一种新型改性的重质碳酸钙方法,使得添加量大于10%左右时甚至更高,降低工业成本,是目前需要解决的问题。
也有一些专利将碳酸钙加入到PBAT/PLA薄膜中,如公开号为CN 113652063的一种碳酸钙填充的PBAT/PLA可降解薄膜及其制备方法 ,专利中采用纳米级碳酸钙和不同的扩链剂、改性剂等助剂混合制备生物可降解薄膜。公开号为CN 103724950 B的 一种含有PBAT的组合物及其制备方法和PBAT保鲜膜,采用为硬脂酸、硬脂酸钠等最常用改性剂改性纳米碳酸钙后制成PBAT复合薄膜。公开号为CN 113801350 A的一种碳酸钙填充PBAT/PLA生物降解塑料薄膜及其制备方法,专利中,则是利用甲基丙烯酸缩水甘油酯和过氧化异丙苯对聚乳酸化学改性,进而进行熔融共混。上述技术中提到的原料需要特殊处理且添加助剂过多,存在PBAT、PLA的相容性和分散性差的问题。
发明内容
本发明提供了一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,以湿法改性方式复合改性重质碳酸钙。样品制备得到后应用于塑料薄膜制品中,具有极佳的力学性能和可生物降解性。
一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,用丙烯酸马来酸共聚物对碳酸钙进行表面湿法改性,再用油酸进行二次改性,制备得到新型复合改性重质碳酸钙;再将聚乳酸、聚对苯二甲酸-己二酸-丁二醇酯、改性重质碳酸钙、扩链剂和抗氧剂熔融共混并切粒,然后进行吹膜,即得复合材料薄膜;具体步骤如下:
(1)称取一定质量的碳酸钙并进行干燥;
(2)将干燥后的碳酸钙粉末加入一定体积的乙醇和水的混合溶液中,升温且进行机械搅拌30min;
(3)将不同含量的丙烯酸马来酸共聚物水溶液加入到上述溶液中,持续搅拌1~5h;
(4)将不用含量的油酸乙醇混合溶液加入到上述溶液中继续搅拌1h;
(5)将上述混合液经过滤、洗涤、干燥后,得到复合改性碳酸钙粉末;
(6)将PLA、PBAT、改性碳酸钙、扩链剂、抗氧剂混合均匀后加入到双螺杆挤出机中挤出造粒,并进行吹膜,即得到改性PLA/PBAT/CaCO3复合材料膜。
优选的,步骤(1)中,所用碳酸钙粉末为未经过任何处理的重质碳酸钙粉末。
优选的,步骤(2)中,乙醇和水的质量比为6:4或7:3,搅拌温度为60℃。
优选的,步骤(3)中,丙烯酸马来酸共聚物质量分数为0.5%-1%,。
优选的,步骤(4)中,油酸的质量分数为0.5%-1.5%。
优选的,步骤(5)中,干燥温度为100℃,干燥时间为12h。
优选的,步骤(6)中,所述PBAT、PLA质量比为6:4,碳酸钙质量比为10%-35%。
优选的,步骤(6)中,所用扩链剂为聚氨酯扩链剂6059,扩链剂剂量为0.2%-0.5%,抗氧剂为抗氧剂1076、抗氧剂626,抗氧剂含量为0.1%-0.5%。
由上述任一项所述的制备方法制得的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法。
与现有技术相比,本发明具有如下优点:
(1)本发明首先对重质碳酸钙进行改性,通过丙烯酸马来酸共聚物和油酸对碳酸钙进行表面改性,相比于直接用未改性的碳酸钙共混,本发明解决了重质碳酸钙在PBAT/PLA复合材料中相容性和分散性差的问题,进而进一步提高了复合材料的力学性能。
(2)本发明利用聚氨酯扩链剂6059进一步提高改性碳酸钙在聚合物基体中的分散性,并且通过增长聚合物基体的碳链,进一步增加了复合材料的力学性能和韧性。
(3)本发明的改性重质碳酸钙在复合材料中填充量达到了30%,大大的降低了生物降解塑料的成本,同时所制备的复合材料塑料具有良好的力学性能和生物降解性能。
(4)本专利相比现有技术采用的则是未经过任何处理得重质碳酸钙,且添加得助剂简单。其用丙烯酸马来酸共聚物和油酸对为进行任何处理的重质碳酸钙进行复合改性,进而和PBAT/PLA进行熔融共混,制得复合改性可生物降解薄膜。本制备工艺简单,所加助剂无毒无害,且添加量少,成本低廉。本专利中制备的改性碳酸钙具有一定的疏水性且表面所携带的官能团能很好的增强与PBAT、PLA的相容性,力学性能也有了很大的提高。
附图说明
图1为实施制备的复合薄膜的XRD图谱。
图2为实施制备的复合薄膜的SEM图谱:(a)10%CaCO3/PBAT/PLA复合薄膜;(b)复合改性10%CaCO3/PBAT/PLA复合薄膜;(c)复合改性30%CaCO3/PBAT/PLA复合薄膜。。
图3为实施制备的改性前后的碳酸钙SEM图谱:(a)对比例1即改性前碳酸钙;(b)改性后碳酸钙。
实施方式
下面通过具体实施例对本发明作进一步的详细说明,但本发明实施方式不限于此。
需要说明的是,无特殊说明外,本发明中用到的各种原材料、试剂、仪器和设备等均可通过市场购买得到或者可通过现有方法制备得到。
实施例
一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,包括如下步骤:
(1)将100g重质碳酸钙粉末加入到500ml的乙醇水溶液中,其中乙醇和水的质量比例为6:4,超声分散后,升温至60℃,加热搅拌30min;
(2)将1%的丙烯酸马来酸共聚物溶于10ml的去离子水中,进行超声分散,并滴入上述溶液中,持续搅拌反应1h;
(3)将1%的油酸溶于10ml的无水乙醇中,进行超声分散,加入上述溶液后,继续搅拌反应1h,待反应完成后抽滤、洗涤、干燥,得到改性重质碳酸钙;
(4)将10%的改性碳酸钙、PBAT、PLA、1份扩链剂、1份抗氧剂1076和抗氧剂626混合均匀后,经双螺杆挤出机熔融挤出、拉条、风冷、造粒,干燥后,得到复合改性重质碳酸钙填充PBAT/PLA复合材料;
(5)将上述复合材料投入单螺杆吹膜机中,吹制成膜,挤出机温度130-190℃,得到重质碳酸钙填充PBAT/PLA生物降解塑料薄膜。
实施例
(1)将300g重质碳酸钙粉末加入到1000ml的乙醇水溶液中,其中乙醇和水的质量比例为6:4,超声分散后,升温至60℃,加热搅拌30min;
(2)将1%的丙烯酸马来酸共聚物溶于20ml的去离子水中,进行超声分散,并滴入上述溶液中,持续搅拌反应1h;
(3)将1%的油酸溶于20ml的无水乙醇中,进行超声分散,加入上述溶液后,继续搅拌反应1h,待反应完成后抽滤、洗涤、干燥,得到改性重质碳酸钙;
(4)将30%的改性碳酸钙、PBAT、PLA、1份扩链剂、1份抗氧剂1076和抗氧剂626混合均匀后,经双螺杆挤出机熔融挤出、拉条、风冷、造粒,干燥后,得到重质碳酸钙填充PBAT/PLA复合材料;
(5)将上述复合材料投入单螺杆吹膜机中,吹制成膜,挤出机温度130-190℃,得到重质碳酸钙填充PBAT/PLA薄膜。
对比例1
(1)将100g重质碳酸钙放入干燥箱中干燥,干燥温度为100℃;
(2) 将10%的未改性碳酸钙、PBAT、PLA、1份扩链剂、1份抗氧剂1076和抗氧剂626混合均匀后,经双螺杆挤出机熔融挤出、拉条、风冷、造粒,干燥后,得到未改性重质碳酸钙填充PBAT/PLA复合材料。
最后需要说明的是:以上实施例不以任何形式限制本发明。对本领域技术人员来说,在本发明基础上,可以对其作一些修改和改进。因此,凡在不偏离本发明精神的基础上所做的任何修改或改进,均属于本发明要求保护的范围之内。
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本发明提到的各个部件为现有领域常见技术,本行业的技术人员应该了解,本发明不受上述实施例的限制,上述实施例和说明书中描述的只是说明本发明的原理,在不脱离本发明精神和范围的前提下,本发明还会有各种变化和改进,这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。
Claims (9)
1.一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其具体方法为,
第一步:用丙烯酸马来酸共聚物对碳酸钙进行表面湿法改性;
第二步再用油酸进行二次改性,制备得到新型复合改性重质碳酸钙;
第三步将聚乳酸、聚己二酸/对苯二甲酸丁二酯、改性重质碳酸钙、扩链剂和抗氧剂熔融共混并切粒,然后进行吹膜,即得复合材料薄膜。
2.根据权利要求1所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,所述聚乳酸为高光纯聚乳酸原料,密度为1.25±0.05g/cm3熔融指数为≧8(190℃/2.16kg)。
3.根据权利要求1所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,所述聚己二酸/对苯二甲酸丁二酯为高光纯聚己二酸/对苯二甲酸丁二酯原料,密度为1.25g/cm3,熔点为110-120℃。
4.根据权利要求1所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,第一步中,按重量份数计,由以下原料组成:丙烯酸马来酸共聚物0.5-2份,重质碳酸钙为10-50份,水和乙醇混合液10-50份。
5.根据权利要求1所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,第二步中,按重量份数计,由以下原料组成:油酸0.5-2份,乙醇混合溶液。
6.根据权利要求1所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,所述助剂包括聚氨酯扩链剂、抗氧剂一种或两种。
7.根据权利要求1所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,第三步中,按重量份数计,有以下原料组成:PBAT40-60份、PLA0-40份、重质碳酸钙粉0-50份、聚氨酯扩链剂0-2份、抗氧剂一种或两种0.1-2份。
8.根据权利要求4所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,乙醇和水的质量比为6:4或7:3。
9.根据权利要求1所述的一种新型复合改性重质碳酸钙用于PBAT/PLA薄膜的制备方法,其特征在于,所述聚乳酸PLA、聚己二酸/对苯二甲酸丁二酯PBAT质量比为6:4,碳酸钙质量比为10%-35%。
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